llilililill[illlllll

Holding it AllTogether
Ancient and Modern Approaches to Joining, Repair and Consolidation
Edited by Janet Ambers,Catherine Higgtt,
Lynne Harrison and David Saunders

71.lrcnetype

lLl
THE

Publications

in association with

BN

ISH MUSTUM

First published 2009 by Archetype Publications Ltd in association with the British Museum Archetype Pubications Ltd. 6 Ertzroy Square

London \)1T 5HJ

www.archetype.co.uk

O 2009 the authors and the

British Museum

ISBN: 978- 1 -90+982- 47 -0

British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library

All rights reserved. No part of this pubication may be reproduced, stored in a retrieval system, or transmitted, in
publishers.

any

form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission of the

The views and practices expressed by individual authors are not necessarily those ofthe editors or the publisher. The editors and the publisher take no responsibility for any harm or damage to collections or health hazards that may be caused by the use or misuse of any information contained herein.

Cover illustrations: all images on the front and back cover also appear in this volume. For descriptions, photograph credits and copyright notices see the following pages:

Front cover: top row (from L to R): Figure 3, p.20I; Figure 3, p. 108; Figure Id, p.206; second row (from L to R): Eigure l, p. 130; Figure 4,p.22; Figure 4b, p.208; thirdrow (from L to R): Figure 4, p. 111; Figure 3,p.122; Figure 1, p.107;fourthrow (fromLto R):Figrre2,p. l87; Figure 5, p.51; Figure 3, p. 180.
Back cover: Frgwe I, p. 167
Typeset by Caz Jones Design, Norwich Printed and bound in Great Britain by Latimer Trend Ltd., Plymouth

Contents

Foreword
Acknowledgements

IX
X1

PART

JOINS AND REPAIRS: ANCIENT AND TRADITIONAL

Glass and ceramics

Ancient glass gluing recipes Gerhard Eggert and Daniela Smone Straub Ancient repairs in archaeological research:
a

Near Eastern perspective

Renske Doojes and Oliver Peter Neuwenhuyse

Joining clay: a comparison of modern and ancient techniques Dean E. Arnold Prehistoric and ethnographic repair techniques and materias on southwestern Native American Chris W'hite, Nancy Odegaard and Arianna Lea Shackle
The use of ethnographic and scientific knowledge to expore creosote lac repairs on pottery vessels at the Arizona State Museum

13

pottery

18

25

Arianna Lea Shackle, Dean Sully, Renata Peters and Chrs \Yhite
Metals
Bronze Age metalwork from central Norway: some examples of ancient and modern repair
t1 JA

Lucy Skinner

interpreting the construction and function ofthe terrets from the Ferry Fryston chariot burial
Sonia O'Connor
Rivets: connection and repair in Mississipian period copper artefacts

atr JJ

42

I(im Cullen Cobb and Thomas Evans

Organics

13,000 year old repair: new observations on a Late Magdalenian spearthrower from Montastruc, Tarn-et-Garonne, France Clare Ward, Janet Ambers and Jill Cook

50

CONTENIS

Continuity or change? The use and function of birch bark tar ln Norwegian Early Iron Age grave Camilla C. Nordby Construction, modification and repair of Mexican mosalcs: evidence from the adhesives
Rebecca J. Stacey and Carolne R.

contexts

54

6l

Cartwright
6B

The historic repair and re-use of Byzantine wooden bookboards in the manuscript collection of the monastery of St Catherine, Sinai

Andrew Honey and Athanasos Velos

The Plkne cruciflx: unusua joinlng materials in a polychrome crucifix from Finand Suv Leukumcavqara
78

Overview
Repalrs in antiquity illustrated by examples from the prehistory of Denmark
Helge Brinch Madsen 83

PART 2 JOINS AND REPAIRS: MODERN (POST NINETEENTH CENTURY)

Modern adhesives
Poly(viny acetate) and acrylic adhesives: a research update
Jane L. Down

9l

Identification of a formuation change in a conservation-grade adhesive Petronella Nel and Deborah Lau
Glass and eramics

99

A history of joining
Sandra Davson

glass fragments

t07

Paraloid B-72@:25 years of use as a consolidant and adhesive for ceramics and glass Stephen P IQob

113

Internal fractures on stalned glass windows:

conservation study

120

Katrn Wttstadt and Peter Mottner

Studies of the degradation of epoxy resins used for the conservation of glass Ins Coutnho, Ana Mara Ramos, Awgusta M. Lma andFrancisco Braz Fernandes

t27

Stone
Never forever: assembly of scupture guided by the demands of disassembly Jerry Podany, Erk Rsser and Eduardo Sanchez
L34

An evaluation of potentia adhesives for marble repair Mersedeh lorjan, George Wheelen Carolyn Riccardell, Wole Soboyejo and Nrna Rahbar Organics
The consolidation of wood with Paraloid B-72@ Irena Kuerov and Daniela Drncovc

143

solutions

150

A study of the effects of PVAC on works of art on paper and wood: pH and colour change Gema Campo Francs, Anna xlualart Torroja, Marta Oriola Folch anc Crstna Ruz Recasens

r57

PART 3 CASE STUDIES

Means, materials and ethics: the conservation of two Egyptian mummies for long-term Jane T. Bouvard and Melangell Penrhys Jones

display

166

CONTENTS

Ancient and modern joining techniques on

E I e n A s d er a k i -Tzo um er k o ti

bronze Helenistic urn

L73

Modelling the Caergwrle bowl: ancient, historic and modern methods Mary Davs and Annette Townsend An investigation of repairs to Chinese bronze artefacts at the Harvard Art Museum Susan D, Costello, I(atherne Eremn and Francesca G. Bewer
Boundaries and authenticity in the Monument to Marchese Spnetta Malaspina Sarah Healey-Dlkes and /onathan l(emp
The mechanical assembly of a Renaissance terracotta relief: restoring a tin glazed work of art Elisabeth Huber Antonio Iaccarno ldelson and. Carlo Serno

177

184

t92

199

Investigation and analysis of historic early twentieth-century Mexican restoration lls and repairs on Casas Grandes ceramics at the Arizona State Museum Caitlin O'Grady

205

vll

Stud ies of the deg radation

of epoxy resrns

used for the conservation of g lass

lns Coutinho, Ana Maria Ramos, Augusta M. Lima

and Francisco Braz Fernandes

filling materials, despite their well-known tendency to yellow. Previous studies have focused on the photodegradation and thermal degradation ofvarious epoxy resins in order to identify those that re most stabe and to elucidate the degradation processes. This studlr concerns the photodegradation of three room-temperature curing epoxy resins - Hxtal NYL-1, Araldite 2020 (XW 396 I XW 397)
ABSTRACT Epoxy resins are rvidely used in the conservation of glass either as adhesives or and Epo-Tek 301

commonly used in the conservation of glass and ceramics. Samples of the three resins were prepared and

exposed to radiation from a xenon arc lamp to simulate the solar spectrum. Colorimetry, differental scanning calorimetry

(DSC), ultraviolet-visible (UV-vis) absorption spectroscopy and tensie strength mechanical tests were used to evaluate optical and mechanical degradation. The results obtained suggest that Hxtal NYL-1 is the least susceptible to lighlinduced deterioration and Epo-Tek 301 is the most light sensitive.
KEYWORDS epoxy resins, glass, photodegradation, tensile strength test, colorimetry,

differential scanning caorimetry, UV-vis absorption spectroscopy

lntroduction for the past

50 years epoxy resins have been used extensively

rn conservation and restoration as adhesives, consolidants and gap filers or a diverse range o materials including stone, metals, ceramics and glass

(Horie 1987; Berducou 1990; Selwitz

1992;Buys and Oa<ley 1993; Feller 1994). In the fie1d of glass conservation, epoxy resins are used mainly as adhesives or filing materials, chiefly because of their qlassy appearance (Davison 2003; I(oob 2006). However, yelorvlng and loss of mechanical properties occurs to a greater or lesser degree with ageing, primarily caused by photochemical reactions (Down 1984, 1986; Bradley 1990; McNeil 1992: 16 18; Feller 1994:Lopez-Ballester et al. 1999). The main aim of this study was to aid in the selection of the most suitable material to use as an adhesive and gap iller in the conservation of a large twentieth-century glass vase decorated with enamels. Two large losses and several fractures severey affected the structura stabiity of this object and its aesthetic value. The material to be used woud thus have to act as a structural support and allow good visual compatibiity Moreover, the lling material should be easy to mould, contract minimally during curlng and be safe for both the conservator and the object. After an exhaustve search for suitable materias, it was concluded that epoxy resins best meet these requirements,

despite their tendency to yellow. They bond easiy to glass, have good mechanica performance when exposed to different temperatures and good chemica resistance against humidity and most sovents (Down 2001). If additives or pigments are used, they can be made to imitate any kind of surface and refractive index. They are also a more user-friendly material to r,r,'ork with than poyurethane resins, which release hazardous vapours (Lastbom et al. 2003). A linear shrin<age as low as 0.5% makes epoxy resins more suitable as a illing material than polyesters and poyacrylates (linear shrinkage of 10-l2o/o; Berducou 1990; Larsen 1979; Billmeyer 1984). In order to select a stable epoxy resin to be used in the conservation of the vase, three room-temperature cure epoxy resins (Hxta@ NYL-1, Araldite@ 2020 (X\(/ 396 / X! 397) and Epo-Tek@ 301) were subjected to accelerated ight ageing and the optica and mechanical degradation phenomena evaluated. One of the objectives was to predict when the yellowing would start to be noticeable. Hxtal NYL-1 resin was chosen on the basis of recommendation and on good results in ageing tests reported in the literature (Down 1984, 1986; Bradey 1990; Marschner 2000; Burck and Bonne 2001; I(oob 2006). Araldite2020 is described by the manufacturer as formulated specircally for use in gass and ceramics and for this reason is widely used by conservators (Burck and Bonne 2001). Epo-Tek 301 epoxy resin is reported to have a relatively fast curing time and has given promising
727

INE5

tOUTINIO, ANA

]VLAR

A RA[/OS, AUGI-]5TA I'/ t IVA AND FRANC 5CO BRAZ FERNANDES

results in published tests (Down 1984, f 986). Many of the

epoxy resins used in earlier tests have nou, been discontinued and repaced with new formulations (as with Araldite 2020) or are now difficult to acquire, making the choice of materials for this study somewhat limited.

The optical and mechanical properties of the aged resins were evaluated after 100, 200 and 300 hours of exposure. Changes in coour wee measured using colorimetry and UV-vis absorption spectroscopy (300-400 nm) and DSC and tensile strength tests were used to evaluate physical and
mechanical alterations. This study also aimed to determine the period of time for which the resins remain stable and when they became visually aged (when yellowing can be noticed with the naked eye). Calculations performed on the cumulative radiation in the soar chamber applying Feller's formula (Feer 1994), showed that 100 hours of exposure in the solar chamber are equivalent to seven years of exposure on an average gaery rvall (Feller quotes the annual exposure on a gallery wal as equivalent to L55% of outdoor exposure), with 200 hours corresponding to 12 years and 10 months and 300 hours to 17 years and 8 months. In order to assess the reproducibiity o the accelerated ageing test, as ony one replicate ofeach resin could be tested for each period of time (because of the lack of space in the ageing chamber), four repicates of Araldite 2020 were prepared and submitted to tensile strength tests.

All three of these materias have been studied previously.

Hxtal NYL-1 has been subjected to accelerated light ageing and characterised by utraviolet-visible (UV-vis) absorption spectroscopy (Down 1986) and bv colorlmetry, Fourier transform infrared (FTIR) spectroscopy and tensile strength tests (Bradley 1990). All of these studies were performed using the resin as a thin lm adhesive. It has also been studied under therma ageing conditions (Down 1984) by UV,vis absorp, tion spectroscopy and subjected to acceerated cyclic agelng simuating summer and winter conditions (anaysed by vlsua evaluation; Marschner 2000). Araldite 2020 has been studied under therma ageing conditions and UV light and cycic ageing conditions in SO, using FTIR as a characterisation method (Lpez-Balester et al. 1999). A further study of Araldite u'ith added Orasol' pigments was undertaken in a cyclic ageing chamber simulating summer and winter conditions and analysed by visua comparison (Burc< and Bonne 2001). Epo-Tek 301 has been studied in thermal and accelerated ageing conditions by UV-vis absorption spectroscopy (Down 1984, 1986). For the work descrlbed here, colorimetry and UV-vis absorption spectroscopy were used to evaluate the colour changes in the aged test pieces. Tensile strength tests were performed to evauate t-re mechanical behaviour before and after the light ageing process. In addition, dierential scanning calorimetry (DSC) was used to compement the other techniques by observing the gass transition temperature (T ). This is the first time this test has been used in this way.

Tensile

strength tests

Tensie strength tests were performed on an AG-5Oi(g NG Shimadzu traction machine, at25"C u'ith a gauge ength of 59.2 mm and a rate o extension of 3 mm/min. The measurements produced had an verage standard deviation of x 3.Sa/o on the values of eongation and stress at break.

Colorimetry Colorimetric measurements were performed using an Avantes

Experimental details

Sample preparation and ageing tests Each of the three epoxy resins chosen for testing was prepared folowing the manufacturers' instructions and poured into silicone castlng moulds in a dumbbel shape 11.5 cm long, 0.37 cm thick and with a 0.6 cm neck width and a maximum width of 1.9 cm. The amounts of resin and catalyst were accurately weighed using an electronic scale (t 0.001 g). The dumbbel shape of the test pieces was dictated by tensile strength test specifications. Four aliquots of each resin were made and cured at room temperature or the time recommended by the manufacturer, with a 15 day margin to
assure tota curing.

absorption spectrophotometer equipped with an integrating sphere and Avasoft 6.2 software. The target area was a circuar spot 10 mm in diameter. The samples were measured on top of the pure white materia normay used for the device's calibra, tion, under the same analytical condltions. Two points were measured per sampe with each result being the average o 1O measurements. The spectrophotometric measurements were converted to CELAB coorimetric parameters for the CIE standard 10'observer under standard iluminant D65.

UV-vis

bso r pti on

spectroscopy

Absorption measurements were made using a Perkin Emerlambda 35 UV-vis spectrometer. The measurements were performed between 300 and 400 nm, as yelowing is caused bl'ar increase oflight absorption at the blue end ofthe visible spec-

For the acceerated light ageing experiment, three replicate samples of each resin were placed into a solar chamber (SoarBox 3000) equipped with a xenon arc lamp and a constant irradiance of 800 W.m 2. The solar box simulates the solar spectrum ltered through ordinary window glass (transmitting above 300 nm). One test piece of each resin was kept in darkness to act as a reference sampe.
128

trum (the colour region complementary to yellow).

Differenti

a I scq n

ni n g colori

metry

Differentia scanning calorimetry mesurements were caLLre out on a Setaram DSC 131 scanning calorimeter equippe..

Table 1 Results ofthe tensile strength tests. Araldite 2020 Time (hrs)
0 100

Epo-Tek 301

Hxtal NYL-1 Time (hrs

300 44.67 5.58 7545.20
0

Time (hrs)
200 300 45.56 6.08 1357.90 0 42.56 43.82 167.83 100 46.77 39.37 775.48 200
48.61.

100 42.56 30.50 201.33

200
43.69 3.58 1741.80

300 34.86

Strength at break (MPa) Elongation at break (%) Yeld stress (MPa) Younq's modulus (MPa)

17.57 46.84 13.60 904.90

22.50

4t.73
7.70

40.46
JJ.JJ

4I.12
915.30

4.39

4.9r
7326.50

726t.80

r875.20

190.63

l C m

o T
Table2L",a",b"andAE*"bvaluesobtainedforthereference(0hrs)
Araldite 2020 Time (hrs)
0

andagedsamples('l00hrs,200hrsand300hrs) ofAraldite2020,Epo-Tek301 andHxtal NYL-1 epoxyresins

Epo-Tek 301 Hxtal NYL-1 b2.16

b2.5

U
m

n
U
I

L86.49

b1.47

T,-

L"
88.67

0.41 Aa* 0.15 0.31 0.51

87.94

o.23

0.11

o
Z AE3.64 2.38
J.JL

AL100 200 300 4.35 4.39

5.6

ab"
5.64 6.15 6.35

AE* 7.12 7.56 8.48

/\t."
5.56 4.82 6.29

Aa"
0.27 0.53 0.54

Ab"
9.23 9.84
8.1

AE* r, 10.78 10.97 10.27

AL3.28
1,.56

Aa*
0.07 0.15 0.26

ab.
L.58

o T
m

t.79
1.15

><

3.1

T m t^

z
C
U

o
F
--l

r m
Table 3 Resin glass transition temperature (Tn) measured by DSC Araldite 2020 Time (hrs)
0
Ts,

o
Epo-Tek 301

Hxtal NYL-1 Time (hrs)

200
300 52.6 0 47.4
100

z.
m

Time (hrs)
200 56.9 300 56.9 0
49.3 100 53.9

n
200 53.4 300
50.2

100 56.9

-1

('C

49.8

54.7

48.6

z.

o T
C)

N)

NS

TOI]I NHo, ANA

I/AR A RAioS AI]GU5TA [/1. L [,']A AND FRANCIS'O BRAZ FERNANDES

abe with photodegradation (McNeill 7992:27-8; Horie 1987). As shown by the resuts in Table 1, this resin has the highest initial Young's modulus of the resins tested but aso has the owest Young's moduus variation found ln the ageing tests (c.400 MPa). It aso has the initial Young's moduus value most unlike that of glass. The resuts obtained from mechanical tests on Epo-Tek 301 resin show that its strength at break and Young's modulus values tend to increase up to 200 hours ageing. During this period, the polvmer is undergoing an increase in crossllnking, as also suggested by the decreasing elongation at break values. However, after 300 hours ageing, it shows a decrease ln both strength at break and Young's modulus, suggesting a change in degradation mechanism from increasing crosslinking to chaln scission. The elongation at break value also increases slighty as the resin becomes hard and consequenty more flexible. As shown in Table 1, Epo-Tek 301 has the lowest initia Young's moduus of any of the resins tested. It is therefore the most elastic of the three, with the initial vaue most similar to that of gass (although still approximately twice the value). This resin aso shows the highest degree of variation in Young's modulus (c.940 MPa), meaning that this is the resin that shows the most physical changes r,r,ith photodegradation. For Hxtal NYL-1, the values of both Young's modulus and strength at break increase until 200 hours exposure. This behaviour can aso be explained by an increase in the polymer cross-linking due to photodegradation. As expected, the values ofthe elongation at break decrease due to the net enhancement ol polymer rigidity. The mechanical data from the 300 hours ageing test shows a possibe change in the process of degradation similar to that observed r,r'ith Epo-Tek 301. Thls hypothesis is supported by the decrease in the strength at break and Young's modulus values when compared to the 200 hours sample results. An increase in the elongatlon at brea< is also observed due to the greater flexibility of the broken polymer chains. Overal this test shows that the photodegradation ofthe resins is not a lin-

E@
,

\;; \d
t

l:,

@
{i \/-

i$*5 t$Is

;)'

;:.t;

\*l \/
(1

Figure 1 Reference (0 hrs) and aged samples

hrs)

00 hrs,200 hrs and 300

ofAraldite 2020, Epo-Tek 301 and Hxtal NYL-1 epoxy resins.

with

thermal analysis data system. Sampes of 10 mg were

paced in auminium pans and sealed. The samples were heated

from -20"C to 100"C at a rate of 5"C per minute under a nitrogen atmosphere.

Results and discussion

All three resins showed

perceptible colour change with light

exposure, as can be seen in Figure

l.

Tensile

strength test
(E) vaues meas-

In order to interpret the Young's modulus

ured for the resins under study, it is important to keep in mind the equivalent value for gass. According to the literature, the theoretica Young's moduus of glass varies between 61 and 75
GPa depending on chemical type. These vaues were calculated

ear function with time (Down 1984, 1986). Only one yield stress measurement is given (for Araldite 2020) in Tabe 1 as all the other resin samples fractured before this point. This suggests that the non-aged Araldite 2020 sample has a lower degree ofcross-inklng than the corresponding

non-aged Epo-Te< 301 and Hxtal NYL-1.

from the energy required to break the Si-O bonds (Fernandes 1999; Navarro 1991). The measured glass Young's modulus is about 50 MPa, some thousand times lower (Fernandes 1999; Navarro 1991). For the follon,ing discussion the measured value (50 MPa) wi be that considered. The results obtained for the reference and the three aged replicates of each epoxy resin are reported in Table l. For Araldite 2020 the strength at break values tends to increase during the ageing test periods. This tendency is also observed ln the Young's modulus values. This material response to the mechanical tests can be explained as an lncrease in chain cross,linking due to the ageing effect of light
in poymers. This degradation mechanism is also confirmed by a decrease in elongation at break values, lvhich occurs because the hardened polymer breaks earlier and becomes less deform,

Colorimetry
The dfference in colour of the samples before and after ageing is reported in Table 2 in terms of L'*, Aa" and Ab'*, where these are the changes in the CIELAB coour coordinates L", a" and b" respectivel,v. The standard deviation of the average value of the two measurements is less lhan 2o/o. The L* coor, dinate expresses the lightness of a material, the b'* coordinate yellow-blue, and the a" coordinate red-green. In this experi, ment, the coours are those of the fim superimposed on the white reference standard. Also reported in Table 2 is the overal colour change 4E",' which is equal to (1-": + a'*2 + It is generally considered that a colour difference of ^b:r)or. greater than 1.5
AE'*.,0

units is visible in samples placed alongside each

130

STI-I

D ES OF THE DEGRADAT ON OF EPOXY RE5 NS USED F'OR TF]E CONSERVATION OF GTASS

other (Ashley-Smith et a\.2002). For this study the change ln b'* coordinate (Ab') was considered the most important as it
expresses the yellowness

ofthe epoxy resins.

As expected, al three epoxy resins showed some degree of yellowing with ageing. Howeve! it is interesting to note that Epo-Tek 301 and Hxtal NYL-1 exhibit an increasing yelowing up to 200 hours of light exposure and a slight decrease in the yellowing intensity at 300 hours. A different pattern was observed for Araldite 2020, which became increasingly yelow up to the end of the experiment. By comparing the Araldite 2020 colorimetrlc values with those from the tensie strength test, it is also possible to see an increase in both Young's modulus and strength at brea< results wlth ageing time. This may indicate that the increase in the yellow coloration of the resin samples is due to greater cross-linking. Of the three epoxy resins tested, Epo-Tek 301 exhibited the greatest degree of yellowing during the ageing experiment. A considerable increase in b" coordinate value occurred up to 200 hours of light exposure. Comparing this wlth the mechanical test resuts previously discussed, the Young's modulus and strength at break values also show a considerable increase to 200 hours and a decrease for the 300 hours sample. Therefore, it is suggested that a change in degradation mechanism occurs, from an increase in cross-linking to a macromolecular chain scission, at between 200 and 300 hours of ageing. Of the three epoxy resins tested, Hxta NYL-l showed the smallest variation in b" coordinate. As discussed above, the greatest value was measured at 200 hours of light exposure, followed by a slight reduction in the yellowing intensity at 300 hours. The same explanation as that suggested for Epo-Tek 301 resin can be used to expain the colour changes of Hxtal NYL1 resin. In both cases the changes in colour and mechanical behaviour were observed to coincidence, indicating a degradation process.

the sampies of the three epoxy resins tested are compared visuay the yellowing of Hxtal NYL-l samples is hardly noticeable with the naked eye (Figure 1) whie the colour change in Araldite 2020 and Epo-Tek 301 samples is very perceptible at 100 hours of light exposure and even greater at the maximum of their b'* variation, 300 hours and 200 hours,
respectively.

'\)hen

UV-v i s a bso r pt

n sp e ct ro sco PY

The UV-vis absorption measurements were performed in the utravioet to bue spectral region (300-400 nm) as the
appearance of an absorption band in this region was expected to suggest that the sample exhibits yellowing (although most of this range is outsde the visible region).

Extrapolation of the UV-vis results suggests results in agreement with the colorimetric results, and in good agreement with the other techniques used (Figures 2, 3 and 4). As can be seen in the figures, the spectra ofthe three resins tested exhibit absorption bands in the 300-400 nm region, -with a greater absorption for the most yellowed samples.

iff e re nti o I sco n n i n g

ca I o r i m

etry

Differentia scanning calorimetry was used to determine the change in glass transition temPerature (\) durinS the ageing
process for the three resins. If the degradation process leads to an increase in cross-linking of the macromolecular chains, \ is expected to increase, as a higher energy is necessary for the first chain movement. If the degradation process is chain scission, T wil drop, as less energy is needed to initiate the chain

movement as the molecular network will be more open.

Araldite 2020
control smple

Epo-tek 301
nfs6l ssrnpls

o -o L o q

I c

1.5

hours 100 hours 200 hours 300

-.
1.s

hours 100
hours 200 hours 300

.o

o (t,
-o

-o1

350

375

350

Wavelength / nm
Figure 2 UV-vis absorpton spectra of Araldite 2020 samples.

Wavelength / nm
Figure 3 UV-vis absorption spectra of Epo-Tek 301 samples.
131

N5

toUI]NIo,

ANA h4AR

A RA/\,lOS, AUGUSTA

[,1

]\IA AND FRANC

5'O

BRAZ FERNANDES

Hxtal NYL-1
control sample

ing with light ageing, which was already perceptible in samples after 100 hours of exposure (the equivent of seven years in a museum environment). Epo-Tek 301 showed the greatest increase in yellowing.

hours 00
hours 200

In terms of mechanical characteristics, the Young's modu,

lus value measured for the three resins before agelng is aready

hours 300

considerably higher than that of g1ass. With agelng, this value increased for all three resins with Araldite 2020 exhibiting the smallest varlation and Epo-Tek 301 the greatest. Overall the results obtained from the accelerated light ageing experiments suggest that Hxtal NYL-1 is the least susceptible to photodegradation of the resins tested and Epo,Tek 301 the most. The accelerated light ageing testing performed was crucial in the seection of Hxtal NYL-1, the most stabe epoxy resin, or use in the conservation of the glass vase.

Wavelength / nm
Figure 4 UV-vis absorption spectra of Hxtal NYL-1 samples.

Acknowledgements
The authors thank the Analytica Services Laboratory of REQUMTE

or differential scanning calorimetry results. Francisco Braz Fern,

The resuts for Araldite 2020 show that the measured T for the non-aged control sampe is 49.8'C (compared with the manufacturer's reported value of 39.5'C). By comparing the values obtained from mechanlcal tests, coorimetry and absorption spectroscopy, it would be expected that T vaues would increase with ageing time, as the resin seems to degrade by an increase ln cross-llnking. However, the observed T" values remained the same, 56.9'C, throughout the agelng period after the first 100 hours. Since Araldlte 2020 is the resin with the lowest varlation in Young's modulus between 100 and 300 hours, it is possible that this variation (the increase of cross-linking) may not be enough to alter the T within this period. The results obtained for Epo,Tek 301 show an initia T of 49.3"C (lower than the value of >65'C quoted in the manufacturer's Technica Data Sheet). Looking at the results from mechanical tests, colorimetry and absorption spectroscopy, the increase in T. to 200 hours, folowed by a decrease at 300 g hours is exactly what would be expected for the degradation process suggested above. The results for Hxta NYL-l show the same pattern, again in line with expectations.
andes ac<nowledges the plurianual funding o CENMAT/I3N by

FCT/MCTES.

Materials and suppliers

Araldite 2020: CIBA Pol1,mg1r, 205 South James Street,

1g$,port 19804-2424, Delar,r'are, USA. Supplied by

Conservation Resources UK Ltd., Unit 2 Ashvile Way, Off !atlington Road, Cowley, Oxordshire OX4 6TU, UK
(wrnrw.conservation-resources.co.uk).

Epo-Tek 301: Epoxy Technology, Inc. 14 Fortune Drive, Billerica, MA 01821-3972. Supplied by Conservation Resources U( Ltd., Unii 2 Ashville \/u)., 01 'Watlington Road, Cowley, Oxfordshire OX4 6TU, UK
(rvww.conservation-resources.co.uk). Hxta NYL-1: Conservation Resources UI( Ltd., Unlt 2 Ashville '!.ay, Off Watlington Road, Cowley, Oxordshire OX4 6TU, UK www.conservation-resources.co.uk).

References
Ashley-Smith, 1., Derbyshire, A. and Pretzel,8.2002. 'The continuing development of a practical lighting policy for works of art on paper

Conclusions
This accelerated light ageing experiment aowed a good comparison to be made of the optical and mechanical degradation properties of three o the most common epoxy resins used for glass conservation

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In terms of optica changes, Hxtal NYL-1 showed the

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Authors'addresses
Principal author for correspondence: Ins Coutinho, Department of Conservation and Restoration, Faculdade de Cincias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal (inesarcoutinhoPgmail.com). Ana Maria Ramos, REQUIMTE-CQFB, Faculdade de Cincias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparca, Portugal (ana.ramos@dq.unl.pt). Augusta M. Lima, Department of Conservation and Restoration and Research Unit 'Vidro e Cermica para as Artesi Faculdade de Cincias e Tecnologia, Universidade Nova de Lisboa,2829-516 Caparica, Portugal (arlgfct.unl.pt). Francisco Braz Fernandes, Department of Materials Science, CENIMAT / I3N, Faculdade de Cincias e Tecnologia, Universidade Nova de Lisboa, 2829-5 l6 Caparica, Portugal (bfpfct.unl.pt).

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